CN1094995A - The preparation method of superstrong acid of carried oxide system - Google Patents

The preparation method of superstrong acid of carried oxide system Download PDF

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CN1094995A
CN1094995A CN 93104882 CN93104882A CN1094995A CN 1094995 A CN1094995 A CN 1094995A CN 93104882 CN93104882 CN 93104882 CN 93104882 A CN93104882 A CN 93104882A CN 1094995 A CN1094995 A CN 1094995A
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郝玉芝
汪颖
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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China Petrochemical Corp
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A kind of preparation method of support type zirconia system super acidic catalyst is that zirconates is dissolved in deionized water or the ethanol water, adds 80-200 purpose r-Al 2O 3Or do not have a sodium silica, regulate the pH value to 6-7 with ammoniacal liquor, generate zirconia coating at carrier surface, then after filtration, washing, dry, soak SO 4 2-, step such as roasting makes ZrO 2-r-Al 2O 3Or there is not sodium silica/SO 4 2-The system super acidic catalyst.This catalyst is than the isomerization reaction activity height of the support type zirconia super acidic catalyst that makes with mechanical mixing and coprecipitation to linear paraffin.

Description

The preparation method of superstrong acid of carried oxide system
The invention relates to oxide-carrier/SO 2- 4The preparation method of system super acids is specifically about zirconium, titanium, ferriferous oxide-r-Al 2O 3Or there is not sodium silica/SO 2- 4The preparation method of system super acids.
Super acids is the acid stronger than sulfuric acid, they are very strong to the positively ionized ability of organic compound, at room temperature but the organifying compound carries out reactions such as alkylation, isomerization, in addition can make to ionic reaction almost the saturated hydrocarbons of non-activity at room temperature react.The liquid acid that replaces present industrial use with solid super-strong acid is carried out catalytic reaction, can avoid equipment corrosion and environmental pollution, product is easy to separate with catalyst, therefore, solid super acid catalyst is considered to one of promising catalyst (Kazusli Arata in the present petrochemical industry, Advance in Catalysis.Vol, 37, P165).Solid super-strong acid is bigger in industrial using value, and at present common have two classes: a class is halogen-containing super acids, because of halogen easily runs off, etching apparatus, therefore, the solid super-strong acid MxOy/SO of the another kind of non-halogen that now generally begins one's study 2- 4, as ZrO 2/ SO 2- 4, TiO 2/ SO 2- 4, SnO 2/ SO 2- 4Deng.As everyone knows, the catalyst that much is used for petroleum refining industry is made up of active component and carrier, with the caking property of increase catalyst and the dispersiveness of active component.Carriers such as aluminium oxide, silica are used to prepare the support type super acidic catalyst, and existing report in the document is as the second-class (Japan Patent: flat 2-71840) adopt coprecipitation to prepare ZrO-Al of northern field person of outstanding talent 2O 3/ SO 2- 4The support type super acidic catalyst is used for the alkylated reaction of iso-butane and cis-2-butene, but its C + 5Yield and purpose product selectivity all are not so good as pure ZrO 2/ SO 2- 4Catalyst is good.S.Soled etc. have reported and precipitated zirconium hydroxide on silica gel, preparation ZrO 2-SiO 2/ SO 2- 4Super acidic catalyst is used for the butene dimerization reaction, and its reaction conversion ratio does not have pure ZrO yet 2/ SO 2- 4Super acids active high (Preprints-American ChemicalSociety, 1992,722).Adopt the support type super acids of mechanical mixing and coprecipitation preparation to be used for n-C 6Isomerization reaction, conversion ratio have only the heavy % of 1-2, and mainly are pyrolysis products, and isomerized products seldom even does not have.
The objective of the invention is on the basis of existing machinery mixing method and coprecipitation, to improve, provide a kind of at r-Al 2O 3Or do not have sodium silica support surface generation zirconium hydroxide coating, the method for preparing super acids then routinely makes support type zirconia super acidic catalyst, to improve the linear paraffin isomerization reaction activity.
Method provided by the invention is that zirconates is dissolved in deionized water or the ethanol water, adds 80-200 purpose r-Al 2O 3Or do not have a sodium silica, regulate pH value to 6-7 with ammoniacal liquor, generate the zirconium hydroxide coating at carrier surface, then after filtration, washing, dry, soak SO 2- 4, step such as roasting makes ZrO 2-r-Al 2O 3Or there is not sodium silica/SO 2- 4The system super acidic catalyst, concrete steps are as follows:
1, the preparation of zirconium salt solution is dissolved in zirconates in deionized water or the ethanol water, and making zirconates concentration is the solution of the heavy % of 20-80;
2, with r-Al 2O 3Or do not have the sodium silica and join in the zirconium salt solution, make ZrO in the catalyst 2Content is the heavy % of 10-90 by amount of calculation, preferably the heavy % of 20-70;
3, under agitation, the ammoniacal liquor of 4 heavy % being added drop-wise in the 2nd step gains, is 6-7 up to PH, makes carrier surface generate the zirconium hydroxide coating, leaves standstill, aging, is washed till no Cl with deionized water -,, make uniform zirconium hydroxide-carrier granular in 100-120 ℃ of oven dry;
4, soak SO with saturated infusion process 2- 4, make SO in the catalyst 2- 4Content is the heavy % of 5-30, and preferably 8-20 weighs %, drying;
5, at 500-700 ℃ of roasting 0.5-5 hour.
The said r-Al of the present invention 2O 3Or the granular size of not having the sodium silica is the 80-200 order, preferably the 100-200 order.R-Al 2O 3Precursor be α-Al 2O 3H 2The O(boehmite).
The said zirconates of the present invention is meant the zirconates that can be dissolved in deionized water or ethanol water, as ZrOCl 28H 2O, ZrO(NO 3) 2, Zr(NO 3) 4Deng, said SO 2- 4The source is (NH 4) 2SO 4Or H 2SO 4Solution.
When adopting the method for the invention to prepare support type zirconia super acids, if soaking SO 2- 4Before, soak the noble metal (catalyst relatively) of the heavy % of 0.1-2.5, after 550-700 ℃ of roasting 0.5-5 hour, again at H 2In 200-350 ℃ of reduction 0.5-2 hour, can make noble metal support type zirconia super acidic catalyst under the atmosphere, this catalyst can further improve the linear paraffin isomerization reaction activity.The said noble metal of the present invention is Pt, Pd or the mixture of the two, and the precursor of said noble metal is H 2PtCl 6Solution or with PdCl 2Be dissolved in the H that makes in the hydrochloric acid 2PdCl 4Solution also can be the two mixture or Pt 4+, Pd 2+The ammino-complex form.
The present invention mentioned soaks SO 2- 4And noble metal, can step impregnation, also can a step dipping, can also soak SO earlier 2- 4, soak noble metal again after the roasting.
The said preparation method of the present invention also can be used for Fe 2O 3-carrier/SO 2- 4, TiO 2-carrier/SO 2- 4, SnO 2-carrier/SO 2- 4Preparation etc. oxide carried type super acids.
The said ethanol of the present invention can replace with other the alcohol that can dissolve zirconates, also can replace with acetone or benzene.
Adopt the support type zirconia super acidic catalyst of the present invention's preparation, if the heavy % in zirconia content in the catalyst＜43, ZrO 2At r-Al 2O 3Can form individual layer branch dissipating bind on the carrier
The support type zirconia super acidic catalyst that employing the present invention makes is to C 5/ C 6When carrying out isomerization reaction, conversion ratio with etc. the ZrO of weight 2/ SO 2- 4The system super acids is suitable, but the mol ratio of the former isomerized products and pyrolysis product is about 0.64-1, if supported noble metal (as 0.5 heavy %Pt), this ratio can reach more than 12, and the latter has only about 0.3.Adopt the support type super acids of mechanical mixing and coprecipitation preparation, reactivity is very low, as on the pulse reaction device, 200 ℃, to n-C 6Carry out isomerization reaction, conversion ratio has only the heavy % of 1-2, and mainly is pyrolysis product, and isomerized products seldom even does not have.And the support type super acids that makes with the present invention, under similarity condition, conversion ratio is the heavy % of 30-35, the mol ratio of isomerized products and pyrolysis product is 0.66-0.64, and this illustrates that the support type zirconia super acidic catalyst that makes with the present invention is than the isomerization reaction activity height of the support type zirconia super acidic catalyst that makes with mechanical mixing and coprecipitation to linear paraffin.
Following example will the invention will be further described.
Example 1
With 40 gram ZrOCl 28H 2The O(Beijing Chemical Plant, AR, down with) be dissolved in the deionized water, make and contain ZrOCl 2Be the solution of 40 heavy %, take by weighing 5 gram 140-200 purpose r-Al then 2O 3(the SB powder that the Zhou village catalyst plant generates, its chemical composition is α Al 2O 3H 2O becomes r-Al after roasting in 600 ℃, 2 hours 2O 3) join in the zirconium salt solution, stirring drips the ammonia spirit of 4 heavy % down, up to PH=6-7, makes carrier surface generate the zirconium hydroxide coating, leaves standstill, wears out 1 hour, is washed till no Cl with deionized water -,, make about 70-80 purpose Zr(OH in 100-120 ℃ of drying 24 hours) 4-Al 2O 3Particle.Take by weighing this particulate samples 5 grams, soak 28 heavy %(NH with saturated infusion process 4) 2SO 42.5 milliliters of solution, under agitation oven dry in 600 ℃ of roastings 2 hours, makes catalyst A.
Example 2
The preparation method just soaks 40 heavy %(NH with example 1 4) 2SO 42.5 milliliters of solution make catalyst B.
Example 3
The preparation method just adds 30 gram r-Al with example 1 2O 3, make catalyst C.
Example 4
The preparation method just adds 20 gram r-Al with example 1 2O 3, soak (the NH of 40 heavy % 4) 2SO 42.5 milliliters of solution make catalyst D.
Example 5
The preparation method just is dissolved in zirconates in the ethanol water that water content is 50 heavy % with example 1, makes catalyst E.
Example 6
The preparation method does not just have sodium silica (Zhou village catalyst plant) with 5 gram 140-200 purposes and replaces r-Al with example 1 2O 3Make catalyst F.
Example 7
The preparation method is with example 6, and just adding 5 gram 100-140 purposes does not have the sodium silica, makes catalyst G.
Comparative Examples 1
The preparation method is with example 1, and just no carrier added floods 2.5 milliliter 20 heavy %(NH 4) 2SO 4Solution makes pure ZrO 2/ SO 2- 4Super acidic catalyst H.
Comparative Examples 2
Adopt mechanical mixing to prepare support type zirconia super acidic catalyst.The pure ZrO that Comparative Examples 1 is made 2/ SO 2- 4Super acidic catalyst porphyrize (＜200 order) is got this powder 2 grams, adds r-Al again 2O 3Powder 2 gram (＜200 order), mechanical mixture, is sieved into 60-80 purpose particle at compressing tablet, makes catalyst I.
Comparative Examples 3
Adopt coprecipitation to prepare support type zirconia super acidic catalyst.
With zirconium salt solution (consumption and concentration are with example 1) and aluminum salt solution (chemical plant, Kingsoft, Shanghai, AR, AlCl 36H 2O 48 restrains and is dissolved in the deionized water, and making concentration is the aluminum salt solution of 40 heavy %) be added drop-wise to simultaneously in the 1 liter deionized water, regulate pH value with the ammoniacal liquor of 4 heavy %, make constant generation of pH value precipitate, filter at 7-8, be washed till no Cl with deionized water -, in 100-120 ℃ of oven dry, porphyrize takes by weighing this sample 5 grams to the 40-80 order, soaks 40 heavy %(NH 4) 2SO 42.5 milliliters of solution in 600 ℃ of roastings 2 hours, make catalyst J.
Example 8
The preparation method is just soaking (NH with example 1 4) 2SO 4Before the solution, soak the H of 2.5 milliliter of 1 heavy % earlier 2PtCl 6Solution, 600 ℃ of roastings after 2 hours in 300 ℃ at H 2Reduction is 1 hour under the atmosphere, makes catalyst K.
Example 9
With the basic composition of conventional chemical assay catalyst A-K, the acid strength with n-butylamine titration method mensuration catalyst the results are shown in Table 1.
(n-butylamine titration method: make indicator with nitrobenzene, make the solvent of indicator with benzole soln).
Fig. 1 has described catalyst B, C, D and measured 2 θ=30-50 ° x-ray diffraction pattern on the x-ray diffraction instrument, and 75 heavy %, 33 heavy %, 43 heavy % represent the ZrO of catalyst B, C, D respectively among the figure 2Content.
Fig. 1 shows, ZrO in catalyst 2When content is lower than 43 weight %, on the X-ray diffraction pattern, do not see ZrO 2The peak, this illustrates ZrO 2At r-Al 2O 3Formed the individual layer dispersed structure on the carrier.
Example 10
Evaluation with the support type super acidic catalyst of the present invention preparation to n-C 6Isomerization reaction activity.
On the pulse reaction device, with n-C 6Be raw material, the isomerization reaction activity of evaluate catalysts A-K.Reaction condition: 200 ℃ of reaction temperatures, 40-80 purpose catalyst 0.4 gram, carrier gas H 2Flow be 50 ml/min, reaction result sees Table 2.
As can be seen from Table 2: the support type zirconia super acidic catalyst that adopts the present invention's preparation is on the pulse reaction device, and 200 ℃ to n-C 6When carrying out isomerization reaction, conversion ratio with etc. the pure ZrO of weight 2/ SO 2- 4The system super acids is suitable, but the mol ratio of the former isomerized products and pyrolysis product is 0.64-1, and shown in catalyst A-G, if supported noble metal Pt0.5 is heavy %, this ratio reaches more than 12, and as catalyst K, and the latter has only about 0.3, as catalyst H.Adopt support type super acidic catalyst I, the J activity of the preparation of mechanical mixing and coprecipitation very low, as on the above-mentioned reaction unit and under the similarity condition to n-C 6When carrying out isomerization reaction, conversion ratio has only the heavy % of 1-2, and mainly is pyrolysis product, does not have isomerized products.And the support type zirconia super acidic catalyst C, the D that make with the present invention, n-C 6Conversion ratio be the heavy % of 30-35, the mol ratio of isomerized products and pyrolysis product is 0.66-0.64.This illustrates that the support type zirconia super acidic catalyst that makes with the present invention is than the isomerization reaction activity height of the support type zirconia super acidic catalyst that makes with mechanical mixing and coprecipitation to linear paraffin.
(annotate: listed SiO in the table 1 2Be meant no sodium SiO 2).
Figure 931048826_IMG1
Figure 931048826_IMG2

Claims (10)

1, a kind of preparation method of support type zirconia super acidic catalyst is characterized in that:
(1) zirconates is dissolved in deionized water or the ethanol water, making zirconates concentration is the solution of the heavy % of 20-80;
(2) with 80-200 purpose r-Al 2O 3Or do not have the sodium silica and join in the zirconium salt solution, make that zirconia content is the heavy % of 10-90 by amount of calculation in the catalyst;
(3) stirring is added drop-wise to the ammoniacal liquor of 4 heavy % in (2) gains down, is 6-7 up to PH, makes carrier surface generate the zirconium hydroxide coating, leaves standstill, wears out, washes no Cl with deionized water -,, obtain uniform zirconium hydroxide-carrier granular in 100-120 ℃ of oven dry;
(4) soak SO with saturated infusion process 2- 4, make SO in the catalyst 2- 4Content is the heavy % of 5-30, drying;
(5) at 550-700 ℃ of roasting 0.5-5 hour.
2,, it is characterized in that r-Al in (2) according to the described method of claim 1 2O 3Or the granular size of not having the sodium silica is the 100-200 order.
3, according to the described method of claim 1, it is characterized in that according to (2) r-Al 2O 3Or do not have the sodium silica and join in the zirconium salt solution, make that zirconia content is the heavy % of 20-70 by amount of calculation in the catalyst.
4,, it is characterized in that soaking SO according to (4) according to the described method of claim 1 2- 4, make SO in the catalyst 2- 4Content is the heavy % of 8-20.
5, according to the described method of claim 1, it is characterized in that r-Al 2O 3Precursor be α Al 2O 3H 2O.
6,, it is characterized in that said zirconates is meant ZrOCl according to the described method of claim 1 28H 2O, ZrO(NO 3) 2, Zr(NO 3) 4
7, method according to claim 1 is characterized in that said SO 2- 4The source is (NH 4) 2SO 4Or H 2SO 4Solution.
8, method according to claim 1, preparation noble metal support type zirconia super acidic catalyst is characterized in that soaking SO according to (4) 2- 4Soak noble metal, making in the catalyst bullion content is the heavy % of 0.1-2.5 before, according to (5) after 550-700 ℃ of roasting 0.5-5 hour, again at H 2Reduced 0.5-2 hour in 200-350 ℃ under the atmosphere.
9, method according to claim 8 is characterized in that said noble metal is Pt, Pd or the mixture of the two.
10, according to Claim 8 or 9 described methods, it is characterized in that said noble metal source is H 2PtCl 6Solution or with PdCl 2Be dissolved in the H that makes in the hydrochloric acid 2PdCl 4Solution also can be the two mixture or Pt 4+, Pd 2+The ammino-complex form.
CN93104882A 1993-05-11 1993-05-11 Method for preparation of superstrong acid of carried oxide system Expired - Fee Related CN1040846C (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
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CN1076634C (en) * 1998-08-27 2001-12-26 中国石油化工集团公司 Process for preparing carried superstrong solid acid
CN1087660C (en) * 1996-07-15 2002-07-17 中国科学院大连化学物理研究所 Catalyst for isobutane preparing reaction by normal butane isomerization and its use
CN100441299C (en) * 2005-11-15 2008-12-10 上海中远化工有限公司 Zirconium dioxide loaded microsphere type silica gel superstrong acid catalyst
CN100556544C (en) * 2007-07-17 2009-11-04 华东理工大学 A kind of preparation method of high isomerization active solid super acidic catalyst
WO2012048533A1 (en) * 2010-10-13 2012-04-19 中国石油化工股份有限公司 Catalyst for selective paraffin isomerization and preparation method and use thereof
CN114733501A (en) * 2022-03-17 2022-07-12 西安热工研究院有限公司 Solid urea hydrolysis catalyst and preparation method thereof
CN115501891A (en) * 2021-06-23 2022-12-23 中国石油化工股份有限公司 N-tetracarbon hydrocarbon isomerization catalyst and preparation method and application thereof

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CN1013361B (en) * 1987-03-13 1991-07-31 中国科学院大连化学物理研究所 Catalyst containing pt, sn, li, s for dehydrogenation of saturated hydrocarbon
DE68925767T2 (en) * 1988-08-30 1996-08-14 Union Carbide Corp Catalysts for the production of ethylene oxide and processes for their production
SE464688B (en) * 1989-02-27 1991-06-03 Eka Nobel Ab CATALYST FOR REDUCING NITROGEN OXIDES AND USING THEREOF

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1087660C (en) * 1996-07-15 2002-07-17 中国科学院大连化学物理研究所 Catalyst for isobutane preparing reaction by normal butane isomerization and its use
CN1076634C (en) * 1998-08-27 2001-12-26 中国石油化工集团公司 Process for preparing carried superstrong solid acid
CN100441299C (en) * 2005-11-15 2008-12-10 上海中远化工有限公司 Zirconium dioxide loaded microsphere type silica gel superstrong acid catalyst
CN100556544C (en) * 2007-07-17 2009-11-04 华东理工大学 A kind of preparation method of high isomerization active solid super acidic catalyst
WO2012048533A1 (en) * 2010-10-13 2012-04-19 中国石油化工股份有限公司 Catalyst for selective paraffin isomerization and preparation method and use thereof
US9314781B2 (en) 2010-10-13 2016-04-19 China Petroleum & Chemical Corporation Catalyst for selective paraffin isomerization and preparation method and use thereof
CN115501891A (en) * 2021-06-23 2022-12-23 中国石油化工股份有限公司 N-tetracarbon hydrocarbon isomerization catalyst and preparation method and application thereof
CN115501891B (en) * 2021-06-23 2023-09-29 中国石油化工股份有限公司 N-carbon tetra-alkane isomerization catalyst and preparation method and application thereof
CN114733501A (en) * 2022-03-17 2022-07-12 西安热工研究院有限公司 Solid urea hydrolysis catalyst and preparation method thereof
CN114733501B (en) * 2022-03-17 2023-09-22 西安热工研究院有限公司 Solid urea hydrolysis catalyst and preparation method thereof

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